N-isopropyl-o-ethyl-o-arylphosphoric acid ester amides

ABSTRACT

N-ISOPROPYL-O-ETHYL-O-ARYLPHOSPHORIC ACID ESTER AMINES, I.E. N-ISOPROPYL-O-ETHYL-O-(3-METHYL-4-METHYL SULFONYL- AND SULFOXY-PHENYL)-PHOSPHORIC ACID ESTER AMIDES WHICH POSSESS NEMATOCIDAL, ARTHROPODICIDAL, ESPECIALLY ACARICIDAL AND INSECTICIDAL, PROPERTIES AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent Oflice Patented Jan. 9, 1973 3,709,961 N-ISOPROPYL-O-ETHYL-O-ARYLPHOSPHORIC ACID ESTER AMIDES Gerhard Schrader, Wuppertal-Cronenberg, and Bernhard Homeyer, Opladen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed June 17, 1970, Ser. No. 47,137 Claims priority, application Germany, July 4, 1969,

P 19 34 001.3 Int. Cl. C0715 9/12; Atlln 9/36 U.S. Cl. 260-949 3 Claims ABSTRACT OF THE DISCLOSURE N-isopropyl O ethyl O arylphosphoric acid ester amides, i.e. N-isopropyl O ethyl-O-(3-methyl-4-methyl sulfonyland sulfoxyl-phenyl) phosphoric acid ester amides which possess nematocidal, arthropodicidal, especially acaricidal and insecticidal, properties and which may be produced by conventional methods.

The present invention relates to and has for its objects the provision of particular new N-isopropyl-O-ethyl-O- arylphosphoric acid ester amides, i.e. N-isopropyl-O-ethyl- O- (3-methyl-4 methyl sulfonyland sulfoxylphenyl)- phosphoric acid ester amides, which possess nematocidal, arthropodicidal, especially insecticidal and acaricidal, properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. nematodes and arthropods with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known that O-alkyl-O-phenylphosphoric acid ester amides, for example O-isopropyl-O-(3-methyl-4-methylmercaptophenyl)-phosphoric acid ester amide (A), O- methyl-O-(3-methyl 4 methylmercaptophenyl)-N-methylthiophosphoric acid ester amide (B) and N,N-dimethyl-O-methyl-O-(3 methyl 4 mercaptomethylphenyl)- thiophosphoric acid ester amide (C) are effective as contact and systemic insecticides. On the other hand, 0,0- dialkyl O arylthionophosphoric acid esters, such as 0,0-diethyl-O-(2,4-dichlorophenyl) thiophosphoric acid ester (D) exhibit a good nematocidal activity [cf DAS (German published specification) 1,121,882 and U.S. patent specification 2,761,806].

It has now been found, in accordance with the present invention, that the particular new N-isopropyl-O-ethyl-O- phenylphosphoric acid ester amides of the formula in which n is 1 or 2, exhibit strong nematocidal, in particular soil-nematocidal, and arthropodicidal, especially insecticidal and acaricidal properties.

The invention also provides a process for the production of a N-isopropyl-O-ethyl-O-phenylphosphoric acid ester amide of the Formula I in which a N-isopropyl-O- ethylphosphoric acid ester amide halide of the formula is reacted, in the presence of an acid-binding agent, with a 3-methyl-4-methylsulfoxylor -4-methylsulfonyl-phenol of the formula In the above formulae, n is the same as defined above, while Hal stands for halogen, preferably chlorine or bromine.

Surprisingly, the N-isopropyl-O-ethyl O phenylphosphoric acid ester amides of the invention are distinguished by a considerably higher nematocidal activity then the known 0,0-dialkyl-O-(2,4-dichlorophenyl) thionophosphoric acid esters of analogous constitution and the same direction of activity. The compounds according to the present invention therefore represent a valuable contribution to the art.

If N-isopropyl O ethylphosphoric acid ester amide chloride and 3-methyl-4-methylsulfonylphenol are used as starting materials, the reaction course can be represented by the following formula scheme:

41 noQ-sm-cm acid-binding agent The starting materials to be used according to the process are clearly defined generally by the Formulae II and III above. The phosphoric acid ester amide halides of Formula II above are known from the literature and are readily accessible, even on an industrial scale, according to customary methods, while 3-methyl-4-methyl sulfoxylor sulfonyl-phenol (III) can be prepared by oxidation with hydrogen peroxide under suitable reaction conditions.

The preparative process is preferably carried out in the presence of a solvent (this term includes a mere diluent). As such, all inert organic solvents are suitable. Preferred examples include aliphatic and aromatic (possibly chlorinated) hydrocarbons, such as benzine, benzene, toluene, xylene and chlorobenzene; ethers, such as diethyl ether, dibutyl ether and dioxan; ketones and nitriles, such as acetone, methylethyl ketone, methylisopropyl ketone, methylisobutyl ketone, acetonitrile and propionitrile.

The reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at substantially between about 20 to 120 C., preferably at between about 50 to C.

The reaction is, in general, carried out under normal pressure and, as already mentioned, in the presence of an acid acceptor. As such, all customary acid-binding agents are suitable. Particularly suitable have proved to be alkali metal carbonates and alcoholates, such as sodium and potassium carbonate or methylate and ethylate; further, aliphatic, aromatic and heterocyclic amines, for example triethylamine, dimethylaniline, dimethylbenzylamine and pyridine, and the like.

When the process is being carried out, the reactants may be reacted in equimolar proportion in one of the above-mentioned solvents in the presence of the acid acceptor at the stated temperatures. After the reactants have been combined, the mixture is stirred for a further 2 to 4 hours, then poured into water, extracted with an inert hydrocarbon, preferably benzene, the organic phase is separated and dried and the solvent is distilled off.

The compounds according to the invention are, as already mentioned above, distinguished by outstanding nematocidal properties with only slight toxicity to warmblooded animals. They may therefore be used for the control of nematodes, particularly those of a phytopathogenie nature.

These include, in the main, leaf nematodes (Aphenlenchoides), such as the chrysanthemum foliar nematode (A. ritzemabosi the strawberry nematode (A. fragariae), rice nematode (A. ory'zae), and the like; stem nematodes (Ditylenchus), e.g. the stem nematode (D. dipsaci), and the like; root gall nematodes (Meloidogyne), such as M. arenaria, M. incognito, and the like; cyst-forming nematodes (Heterodera), for example the golden nematode of potato (H. rostochiensis), the sugar beet nematode (H. schachtii), and the like; the free-living root nematodes, e.g. of the genera Pratylenchus, Paratylenchus, Rotylenchus, Xiphinema and Radopholus; and the like.

In addition, the new compounds of the invention have outstanding insecticidal, acaricidal and systemic properties, with only slight phytotoxicity.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chlo ride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.) and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolines, alumina, silica, chalk, i.e. calcium carbonate, talc,

,kieselguhr, etc.) and ground synthetic minerals (e.g.

highly dispersed silicic acid, silicates, e.g. alkali silicates, etc); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/ or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolygycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/ or with other known compatible active agents, especially plant protection agents, such as other nematocides, acaricides, insecticides, fungicides, and the like, or herbicides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about (Ll-95% by weight, and preferably 0.5% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0000l20%, preferably 0.01-5% by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surfaceactive agent, such as an emulsifying agent and/ or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.00001-%, and preferably 0.0l95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50- microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liter/hectare are needed, and often amounts only up to about 1 quart/ acre, preferably 2- 1'6 fluid ounces/ acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of active compound or even the 100% active substance alone, e.g. about 20100% by weight of the active compound.

In particular, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. nematodes, arthropods, i.e. insects and acarids, and more particularly, methods of combating at least one of nematodes, insects and acarids, which comprise applying to at least one of correspondingly (a) such nematodes, (b) such insects, (c) such acacrids, and (d) the corresponding habitat thereof, i.e. the locus to be protected, 21 correspondingly combative or toxic amount, i.e. a nematocidally, arthropodically, especially insecticidally or acaricidally, effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, fumigating, and the like.

It will be appreciated by the artisan that when using the instant active compounds against nematodes, such active compounds are preferably uniformly scattered in applied amounts of 5-50 kg. of active compound per hectare and then worked into the soil.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention is illustrated, without limitation, by the following examples:

EXAMPLE 1 Critical concentration test Test nematode: Meloidogyne incognita Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alklaryl polyglycol ether To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added thereto and the reinto water and extracted with benzene, and the benzene phase is separated and evaporated. The yield of N-isopropyl-O-ethyl-O-(3-methyl 4 methylsulfoxyl-phenyl)- phosphoric acid ester amide is 100 g. (63% of the sulting concentrate is diluted with water to the desired 5 theory). The refractive index is n =1.5274. final concentration.

The preparation of the given active compound is inti- EXAMPLE 3 mately mixed with soil which is heavilyinfested with the test nematodes. The concentration of the active compound (CaHPNH 0 in the preparation is of practically no importance; only l l so the amount of active compound per unit-volume of soil, 2 which is given in p.p.m., is decisive. The soil is filled into 021150 5 (1) pots, lettuce is sownin and the pots are kept at a greenhouse temperature of 27 C. After 4 weeks, the lettuce roots are examined for infestation with nematodes, and the 75 g. potassium carbonate and 93 g. N-isopropyl0- degree of effectiveness of the active compound is deterethyl-phosphoric acid ester amide chloride are added to mined as a percentage. The degree of effectiveness is 1QQ% 93 g. 3-methyl-4-methylsulfonylphenol in 500 ml. aceto- When infestation is completely avoided; it is "0% when the nitrile. The mixture is then heated to 60 to 70 C. for 3 infestation is exactly the same as in the case of the control hours, poured into water and extracted with benzene, and plants in untreated soil which has been infested in the same the benzene phase is separated, dried and evaporated. manner. The yield is 140 g. The N-isopropyl-O-ethyl-O-(3-methyl- The particular active compounds tested, the amounts 4-methylsulfonylphenyl) phosphoric acid ester amide applied and the results obtained can be seen (from the folmelts at 77 C. lowing Table 1. a The 3-methyl-4-methylsulfoxylor sulfonyl-phenols re- TABLE 1 Coneen tration Degree oi of active destruccompound tlon in, Active compound (constitution) in, p.p.m. percent 021150 0 2 2.5 100 \H 1. so P-O-Q-S OCH; 0. 625 0 l-C;H1N A} H: CzHso O 1) 5 100 G 2.5 85 PO -S Oz-CH; 1. 26 30 0. 625 0 i-O;H -NH 6 i-C:H1O O (A) 100 100 \H as P-O S OH; 25 50 N (known).

c1130 0 (B) 100 100 \ll 50 9s /POS on. 25 50 CHzNH (known).

01130 S (c 300 100 \II 100 20 P-OQ-S 0H, 50 0 CH N m Ha (known).

C2H5O S 40 98 \II (D) 20 so P-O Cl 12 5g C2H50/ (known).

EXAMPLE 2 quired as starting materials can be obtained for example as follows: 1C3H7NH\(|? CHa sO QQfi /P-OSOCH: I 021150 (I) 2 CH: (IVa) Ha 300 ml. of 35% strength hydrogen peroxide are added,

g. potassium carbonate and 93 g. N-isopropyl-O- ethyl phosphoric acid amide chloride are added to g. 3-methyl-4-methylsulfoxylphenol in 500 ml. acetonitrile. After 3 hours stirring at 60 C., the mixture is poured 75 at 20 to 40 C., to 462 g. 3-methyl-4-methylmercaptophenol dissolved in 1.2 l. of methanol and 15 ml. of sulfuric acid. The mixture is subsequently heated to 60 C. for half an hour, and the sulfuric acid is neutralized with calcium carbonate then the mixture is filtered, the solvent is drawn off from the filtrate, and the residue is recrystallized. The yield is 380 g. The product melts at 123 C.

om-sm-Qon A solution of 200 ml. of 35 %-strength hydrogen peroxide in 200 ml. glacial acetic acid is added, at 50 to 90 C., to 155 g. 3-methyl-4-methylmercaptophienol in 400 ml. glacial acetic acid. The mixture is subsequently heated to 90 C. for 2 hours, the solvent is then drawn oil? and the residue is triturated with petroleum ether. The yield is 140 to 145 g. The melting point of the product is 107 C.

More specifically, it will be realized that all of the foregoing compounds contemplated by the present invention possess the desired selective pesticidal, especially nematocidal, arthropodicidal, i.e. insecticidal or acaricidal, properties for combating nematodes, insects and acarids, and that such compounds have not only a very slight toxicity toward warm-blooded creatures, but also a concomitantly low phytotoxicity.

As may be used herein, the terms arthropod, arthropodicidal and arthropodicide" contemplate specifically both insects and acarids. Thus, the insects and acarids may be considered herein collectively as arthropods to be combated in accordance with the invention, and accordingly the insecticidal and/or acaricidal activity may be termed arthropodicidal activity, and the concomitant combative or effective amount used will be an arthropodicidally efiective amount which in effect means an insecticidally or acaricidally efiective amount of the active compound for the desired purposes.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

8 What is claimed is: 1. N-isopropyl-O-ethyl-O-phenylphosphoric acid ester amides of the formula oinlo 3. Compound according to claim 1 wherein such compound is N-isopropyl-O-ethyl-O-(3-methyl-4-methylsulfonylphenyD-phosphoric acid ester amide of the formula onno o References Cited UNITED STATES PATENTS 3,092,544 6/ 1 963 Naul et a1. 260-949 X 2,916,509 12/ 19 59 Schegk et a1. 260949 3,042,703 7/1962 Schegk et a1. 260-949 FOREIGN PATENTS 1,183,494 12/1964 Germany 260949 LEWIS GOTIS, Primary Examiner A. H. SUTIO, Assistant Examiner US. Cl. X.R.

P0 1050 UNITED gums EATENT OFFICE n r I CEREIFECATE Q1 (IQRREC HQ-N Patent Ne. 3,709,961 Dated January 9- 1973 I invent fl Gerhard Sehrader et .91

it is eer tified that error appeal-5 in the ebove-identified patent and that said Letters Patent are hereby corrected as shown below:

3 CoL 2; line 2 5 (Cornfiound-{Illa} shoqid read Col. 3 lines 53 5.4, eorreet the spelling of "kao-"lins".

Col. '3, line 63,1:qrrect the spellingef "ary1pelyg1y 1",.

col 5 Table i mp m shwld read is V CH O v r" I e A I E CH 7 I Z "CQL 5 Table l,- (Compound D) should read w C H u Signedend sea1ed this 10th dey 5f July- 19.73;

(SEAL) iAtteSt:

iDWARQM'.FLETQHERJR;- Rene Tegtmey er c testlng Offlcer C g Commissioner of Patents 

